Polysulphide plastic and process of making



March ze, 1940. J PAT'mcK 2,195,380

POLYSULPHIDE PLASTIC AND PROCESS 0F MAKING Filed Oct. 18, 1938 INVENTOR fw W ' ATTORN Y Patented Mar. 26, E940 UNITED STATES POLYSULPBIDE PLASTICl AND PROCESS 0F MAKING Joseph C. Patrick, Morrisville, Pa., asslgnor to Thiokol Corporation, Trenton, N. J., a corporation of Delaware Application October 18, 1938, Serial No. 235,804

18 Claims. (Cl. 260-79) This invention relates to polymers and synthetic plastics and is a continuation-impart of my application Ser. No. 727,281 filed May 24, 1934, which in turn is a continuation-impart of my application Ser. No. 627,470 filed August 4, 1932 (now Patent No. 1,962,460 issued June 12, 1934, and reissued March 5, 1935, as ,Reissue Patent 19,487).

It is preferred to produce the nal products of this invention in two stages, (a) an intermediate stage and (b) a final stage. In the intermediate stage the product is potentially reactive. The ultimate properties thereof are inchoate. The intermediate product may be subjected to a further reaction which may be designated curing or vulcanization, whereby the ultimate or inchoate properties are developed.

The present invention includes more especially the process whereby the intermediate material is further reacted, cured or vulcanized, andv in this process the intermediate material is reacted with an oxidizing agent and an acid as hereinafter set forth.

The division or separation of operations above referred to has a number of important. advantages. Not only may the intermediate product be highly purified before converting it into its final form, but that intermediate product may be readily worked in various ways to produce a multitude of different products, as different as phonograph records and coated fabrics. Therefore the intermediate product can be sold in bulk to many different buyers who may use it for many different purposes. The intermediate product can be dispersed in organic solvents'and used as a liquid coating, impregnating and binding material.

The intermediate material may be made in one place and sold in the form of a puried coagulum or dispersion in organic solvents or in other form. The buyers are not burdened with the necessity of carrying out the reactions necessary to produce the intermediate product and are supplied with what to them is a raw material capable of diverse uses.

'Ihis division of operations depends upon the fact that the' invention provides for the production of said intermediate material and that it possesses potential reactivity, i. e. the property of undergoing further reaction when heated with an oxidizing agent and an acid in accordance with the present invention. v

The preparation of the intermediate, potentially reactive or uncured material is preferably effected in an aqueous medium in the presence of a dispersion agent, because this permits the production of the polymer in the form of a latex-like liquid. In this latex-like liquid the intermediate polymer is suspended in an aqueous serum and the size of the particles is so small that substantially complete purification is readily effected by washing the latex with water, the latex possessing the property of mixing with water and thereafter settling out by the action of gravity.4

First, the intermediate polymers and certain processes for producing them will be described. Thereafter, the conversion of these intermediate polymers by a second stage reaction will be described, in which reaction a curing or oxidizing agent and an acid are employed, as previously mentioned. The conjoint use of a curing or oxidizing agent and an acid has been found to produce a marked improvement in the development from the intermediate product of the properties inchoate therein. The curing or oxidizing agent and acid may be incorporated with the intermediate product and sold to a consumer who carries out the curing operation, or the latter may purchase the intermediate product and incorporate the oxidizing agent and acid prior .to curing. Of

course the preparation of the intermediate material and its conversion into the nal product may be carried outby the same party.

PREPARATION or INTERMEDIATE PRODUCT represents structure selected from the groups consisting of two carbon atoms connected by a valence bond and two carbon atoms separated by and joined to intervening structure. Said intermediate product may be prepared by reactions which will now be described, reference being had to the accompanying drawing in which Figs. 1 to 6 show the mechanism of the polysulphide reaction.

-In the polysulphide reaction an alkaline polysulphide is employed which may be derived by the reaction of sulphur with a member of the group consisting of alkali and alkaline earth metals, ammonia and amines, e. g. sodium potassium, lithium, caesium, etc., barium, calcium, strontium, etc., ammonia and ethanolamines and the polysulphide may be a disulphide, trisulphide, tetrasulphide, pentasulphide or hexasulphide, e.' g. NazSx where :z: is an integer of 2 to 6.

In the polysulphlde reaction the molecules of the organic substance become joined together to form a complex pattern or chain, i. e., the relatively smallmolecules of the organic substance- This causes the group s .gsm

to take the place of X1 and a new compound is formed as shown in the equation of Fig. 1.

In this reaction X and X1 are, respectively, any substituents which can be split olf by treatment with an alkaline substance, e. g. halogen, acid sulphate, nitrate, acid phosphate, bicarbonate, formate, acetate, propionate, laurate, oleate, stearate, oxalate, acid malonate, acid tartrate, acid citrate, etc. I

As a result of the reaction of Fig. 1, a molecule is produced having a replaceable substituent X attached to one carbon atom, and a sodium polysulphide radical s (Nag) l attached to another carbon atom.

Owing to the capacity of the sodium to unite with the replaceable substituent X, the compound produced in Fig. 1 has the remarkable ability of uniting with itself, as shown in the equation of Fig. 2.

Moreover, the compound produced as shown in Fig. 2 unites with itself in the same manner and this continues until the size of the molecule is so large that its sluggishness prevents further condensation or self-union.

This ability requires the existence of a sodium polysulphide radical (or its equivalent) on one carbn atom and a replaceable substituent on another carbon atom of the same compound.

If this rule is observed, union of the compound containing said pair of carbon atoms to form a compound containing a tetrad or quartet of carbon atoms does not exhaust the reaction because each terminal carbon atom of this quartet willv also have attached thereto, respectively, a replaceable substituent and a sodium polysulphide radical, so that the quartet or tetrad can form an octad, etc.

This permits a building up of a carbon chain in geometrical progression starting with a compound containing (but not necessarily consisting of) two carbon atoms.

The fundamental requirement is that the starting compound shall have at least two carbon atoms and at least two substituents (which are ultimately split oif) attached to said carbon depending upon whether bon atoms plus a group of sulphur atoms thus:

Where the group of sulphur atoms is the tetrasulphide group. `.This group may be the disulphide group S-S-, the trisulphide group the tetrasulphide group shown above, the pentasulphide group Y an alkaline disulphide, trisulphide, tetrasulphide, pentasulphide or hexasulphide is used.' With this explanation the reaction can be regarded from the mechanical point of view and it is clearest when so regarded. The said unit can be likened to a unit building block with at least two interlocking members on each unit. For example, one of these members may' have a male thread and the other a female thread. 'I'he male member on one unit can then f engage the female member on another unit, so

as to build up a chain or complex structure analagous to the polymer of this invention. There must be at least two of such interlocking members on each unit. Otherwise the length of the chain is limited to a union of two elements.

Referring now to the drawing, the compound shown as produced in Fig. 2 continues to unite with itself until a long chain is built'up having the formula shown in Fig. 3. This then loses its X terminal and acquires SI-I terminals at each end by hydrolysis, as shown in Figs. 4 and 5.

It is desired to carry out the abovereaction in an alkaline dispersion medium as specically illustrated in Example 1 below, and to produce the polymer at the above mentioned stage in the form of a, latex-like liquid from which the polymer maybe separated by various means, e. g. coagulation produced by the addition of acid. 'Ihis latex has the property of mixing intimately with water without dissolving therein and may therefore be washed thoroughly to remove soluble impurities.

Notwithstanding the large size of the molecule produced as indicated in Fig. 5, further increase in size may be caused by employing oxidation, preferably while the product is still in the dispersed form and prior'to the curing step, i. e.

1 While the polymer is still in the intermediate stage.

effective under alkaline conditions, such as hydrogen peroxide; benzoyl peroxide; sodium, potassium, barium and calcium peroxides; pertomas;pernisagmalta. nromateaaaafacro-Y lby already mates, etc. J "1 v:Y -mentlonedff v Whe'n oxidized the. polymershownin Fig'.5 con- 'f In the formula shown in drawing in Fig. 6

` L'of the molecule as muon ,as possible in the-indenses as indicated in Fig. 6 inthe drawing.

the alkaline polysulphide. f

the value ofn is so great that the product is sub- Alkaline polysulphides are themselves'oxidia- ,'stantially and practically a' polymer of the unit ing agents provided an excess be employed over 1 the equimolecular proportions shown-in mg, 1 s .sl I l v termediate stage, because this in conjunction with.

It isg'enerally vdesirable to increase the size 'the subsequentl curing tends* to'develop the de-i theproduct reacts as such. For example, sirable qualities orsmechanicalstrength, elastic'- three'mols 'oi' this unit react with two mola of ity, resistance t0 Chemical# and Solventsetc., t0l 'sodium sulphide according to the following equathe highest degree. f Y tion:

Proof that the reaction occurs by the mecha@v s nism shown and that the products obtained have l ll the formulae shown include the following: j ff IJ'S' +2Nals=3[l |SS]+2Nls4 (a) Taking BB' dichlor ethyl ether as anv ex. s ample, the chlorine of the compound appears quantitatively in the form of sodium chloride a a by-product.v a p (b) After isolating the polymer from the soluble by-products the weight `oi? the polymer is quantitatively equal to the weight of the dichlor ether minus the halogen plus the sulphur from and the resulting product is identical in all itsr properties with the product produced by oxidation of a polyfunctional mercaptan as shown `in Equations 1 to 4 above.

Conversely, the polymer shown in Equation 4 above as produced by oxidation of a polyfunctional mercaptan behaves substantially as a poly (c) The proportion of sulphur in the D0lymer mer of the nit is equal to that in the following formula:

n l tcanaooamsn I?? THF] (d) Attempts to dtermine molecular weight A mol of this unit will react with two atoms of of the polymer shows that it is very high. 'I'hls sulphur as follows: is substantiated by the properties as herein des scribed. [-(l: o-s s]+2s cli-.li s- (e) A polymer having properties identical with l l 'il those obtained by reacting dihalogenated ethyl s ether With Sodium tetl'asulphide can be Obtained and the product obtained is identical in all its by a diierent route, as shown by the following properties with that shown in Fig' 6 of the draw equations, which illustrate the mercaptan reacingA tion mentlqned above: This is further proof that the organic radican U in the polymer, i. e., the carbon radicals, are

(,1) 2(HS'R'SH) +0 HSR s s R SH joined together through a bridge of two surphur where atoms. This bridge is in rmchemical combination, whereas the remaining sulphur atoms in the polysulphide polymer are in labile condition and may be removed by partial desulphurizing agents, for example, alkaline monos'ulphides, alkalies including NaOH and KOH, sulphites, et cetera.

In the above equations, instead of the tetra- The above dimercapto ether may be obtained by reacting BB' dichlor ethyl ether with sodium hydrosulphide NaSH.

(2) 2 (HS.R.S.S.R.SH) +0:

HS.R.S.S.R.S.S.R.S.S.R.SH

sulphides, the di, tri, penta and hexasulphides This continues until a polymer is built up having similarly react. the formula v g 'Ihe fundamental requirement for the reac- (3) HS (RSS) 1 -SH tion shown in Figs. 1 to 6 is an organic compound having at least two carbon atoms and a substituent attached to each of said carbon atoms, which substituent is split oi during the reactions Which occur when said compound is treated with an alkaline polysulphide.

For the mercaptanv reaction it is necessary to have an organic compound having at least two uct Shown in Fig. 6 can be partially desulphur carbon atoms and an -SHgroup attached to ized to produce a product identical with that each of said carbon atoms thus shown at (4) above.' I I The above mercaptan reaction shows that the 118.0 C-sH linkage between the organic carbon radicals is l through a sulphur bridge. These carbon atoms may be adjacent or separat- (f) X-ray examination shows that the dised by intervening Structure tance between the carbon radicals is equalto the Compounds produced by the polysulphjde re Sum of the dlameters of two sulphur atoms' action shown in Figs. 1 to 6 are substantially The two sulphur atoms referred to are bound polymers' of the unit `irmly and form the direct bridge between the (i1-Snor] This on further oxidation gives (4) HS.(RSS)nR.S-S.R(RSS)HS The above compoundI (4) reacts with sulphur to produce a product identical with that shown in Fig. 6 in the diagram and conversely the prodcarbon radicals whereas the remaining sulphur atoms are in labile form and may be removed l are produced where Compounds produced by the meroaptan route are substantially polymers of the unit Polymers of the unit tte-1 contain'l'abile sulphur upon removal of which, as by reaction with reducing or desulphurizing agents, they are converted to polymers of the unit H--a-l and conversely the latter can be converted into the former by reaction with one to four atomic weights of sulphur for each molecular weight of said unit.

Where the said carbon atoms are adjacent compounds produced therefrom are polymers of the unit et+-f1 It has been discovered that great improvements can be effected by opening up the space between said adjacent carbon atoms and inserting therebetween intervening structure. By this means polymers of the unit 'special properties for special uses and the boundaries of utility of the polymers have been greatly extended. This is especially true when, in accordance with -the present invention, said polymers are cured withan oxidizing'agent` and an acid. The invention will be further described by illustrating the production and' properties of polymers where the intervening structure between the pair of reactive carbon atoms is selected from the following classes, it being understood that other intervening structure may'be employed:

a. Ether linkage b. Unsaturated carbon atoms A c. Aromatic structure d. Saturated straight chain carbon atoms e. Saturated branched chain hydrocarbons.

a. Where the intervening structure is or contains an ether linkage When the said pair of carbon atoms are joined to and separated by intervening atomic structure characterized by an ether linkage, certain important advantages are obtained. These advantages relate particularly'to the polymer in its `iinal form, i. e. the form produced by curing the areas'eo intermediate polymer. advantages are in general characterized by a combination of the following properties: elasticity. strength. retention of these properties at 'low temperatures, insolubility in common solvents and resistance todistortion by heat.

A specinc example. for the purposes of illustration, of one method of obtaining a polymer of the )unit [-211 lil-Sink] y where l represents two carbon atoms separated by intervening structure characterized by an ether linkage is a reaction between BB dihalogenated ethyl ether and sodium tetrasulphide. The polymer produced is substantially a polymer of the unit S may be Sz, 8:, S4. Ss or Se, depending on whether an alkaline di, trl, tetra. pentaor hexasulphide is used.

By 4reacting the polymer, where S is 3 to 6, with a reducing or desulphurizing agent, i.y e.. an agentcapable of combining with sulphur, as more fully set forth in my copending application Serial No. 28,614, led June 27, 1935,` the labile sulphur may besremoved and the polymer converted thereby into a polymer of the unit and this may be converted from its disulphide form to the corresponding tri, .tetrapentaor hexasulphide form by heating or reacting one mol of said unit withy one, two, three or four atomic weights of sulphur.

Moreover, a polymer'of the unit may be obtained by a different reaction, i. e.,rby oxidizing BB' dimercapto ethyl ether. The disulphide polymers have certain advantages over the polysulphide polymers.

The general formula for polymers ofthe unit i ll represents carbon atoms separated by and joined to structure characterized by an etherdinkage is ttl-f1 where L represents an oxygen atom or the group R.0.R, Rand R' ybeing respectively albi, aralkyl or aryl radicals.

The reaction betweensodium tetrasulphide and BB' dihalogenated ethyl ether will now be dewhere scribed in detail, it being understood that instead of halogens, numerous other substituents could be used,l (e` g. acid sulphate, acid phosphate, formate, acetate, propionate, acid tartrate, etc. which substituents, like halogen, are split ofi during the reaction). The halogen substituent. speciiically chlorine, is used because of economic reasons.

Example 1.-Into a closed reaction tank suitably equipped with stirring means, pipe coils for steam and cold water and a thermometer, are

mechanical agioaseo placed 2000 liters oi 3-molar sodium tetrasulphide solution. To the polysulphide solution are added with vigorous agitation, kilograms of caustic soda dissolved in liters of water. This is iollowed by the addition of 25 kilograms of crystallized magnesium chloride (MgClnHzO) dissolved in liters of water.

The polysulphide mix is heated to about 135 F. and about 700 kilograms (5 kilogram mols) of BVB dichlor ethyl ether are added 'gradually over a period of about three hours. The rate of addition of the dichloro ether is so regulated as to prevent the temperature of the reaction from going above about 210 F. during the reaction.

When all the chloro ether has been added and the temperature shows a tendency to drop, steam may be admitted to the heating coils and so regulated as to maintain a temperature of from 215 to 220 F. for about three hours, during which time the latex-like dispersion of the polymer is constantly stirred or agitated. The heating step just described is carried out in order that the excess of polysulphide over that actually required to decompose the dichlor ether mayexert a condensing or polymerizing effect on the reaction product as flrst formed, as illustrated in Fig. 6 of the annexed drawing.

The nely divided latex-like dispersion of the polymer may now be freed from water-soluble impurities by any suitable means, such as illtration and repeated washing with water, or it may be washed by repeated settling of the particles and removal of supernatant liquid, followed by resuspension in clean water and repetition of the settling process. The washed latex-like dispersion may now be used in the dispersed form or it may be separated from excess water by filtration and drying to give an elastic mass; or it may be treated with suiilcient dilute acid, tor example dilute hydrochloric, sulphuric or acetic acid, to confer a slight acidity on the latex-like dispersion, whereupon coagulation occurs. The coagulum can be freed from adherent and occluded water by mastication or kneading on rolls or by prolonged drying or by subjecting to pressure.

It will be noted that in the above example six kilogram mols of the polysulphide were used Whereas only about five kilogram mols of the organic reactant were used, leaving about 20 molar per cent excess of the polysulphide. 'I'his procedure provides an excess of polysulphide over that required for decomposition of the organic compound and this excess is available for the second step which results in further polymerization of the product due to the oxidizing effect of the excess polysulphide on the nely divided reaction product.l during the prolonged heating period.

Equimolecular proportions ofthe organic reactant could be used with the polysulphide and after the saponication is complete an additional treatment with more polysulphide could be made. Moreover, the latex could be washed and then further polymerized, e. g. by treatment with a currentof air in an alkaline medium. Sub-` stantially the same result is obtained nally but the method given is considered the most convenient and economical, especially in view of the fact that the excess of polysulphide can be recovered if desired.

In the above example, instead of BB' dichlor ethyl ether, any member selected from the following list can be employed, using the same molecular proportions.

Table I AA' disubstituted ethyl ether..

X.C2H4.O.C2H4.X' BB' disubstituted ethyl ether.

, X.CHz.O.CHz.X'

disubstituted methyl ether.

X.C:H4O.CaH4.O.C 2I-I4.X' disubstituted ethoxy ethyl ether. Xczmsmmx' disubstituted thio ethyl ether.

X.CH:.S.CH2.X

disubstituted thio methyl ethei CH: :contadine.cltocmx'Y Hx l s disubstituted 1,3 methoxy, ,2 dimethyl propane. X.CH2.CIII2.CH2.O.CH2.O.CH2.CH2.CHzX disubstituted dipropyl formal. v

X.CH2.CH2.O.CH2.O.CH2.CH2X' disubstituted diethyl formal.v

X.CH|0.CH,.CH.0CH.

disubstituted dimethoxy ethane.

disubstituted para diethoxy benzene.

` X.CII2O.CI.Ia.CHa.OCI-I.1.X

disubstituted dimethoxy ethane.

X.CH2.CH2.CH2 .S .CH2 .CHz,CHa.X' disubstituted dipropyi thio ether. 1

KOC

pp' disubstituted diphenyl ether.

disubstituted anisole.

disubstituted dibenzyl ether.

x x' )foi l aa' disubstituted diphenyl ether.

XOomonOcmcrLcrn disubstituted para propyl dibenzyl ether.

X.CHz.CHz.SOz.CHz.CH2.X' disubstituted methyl suipnone.

X.CHz.CH2.CH2.SO2LCH:.CH2.CH2.X'

disubstituted dipropyl vsulphone.

' amarillento.om.cH..o.cH,.cmomcnom iy .t

disubstituted dimethoxy tetra ethylene glycol.

'AA' disubstituted propyl ether.

CHLCHLCHz.O,CH2.CHz.CHa i i' Gamma gamma disubstituted propyl ether.

cnaomomoonacnon IBB' disubstituted propyl ether.

oHi.cH.cH,.o.cn.cH..cm

. Ix, alpha beta disubstituted propyl ether.

oH,.cH,.cH,.o.oH.cH=.cH

alpha gamma disubstituted propyl ether.

cntcnicnion.ocacmcmcm i alpha alpha dlsubstauted bum ether.

onion.cnnaocmouomon beta beta. disubstituted butyl ether.

CH..cncmcmomcm.onen.

i 4 if gamma gamma disubstituted butyl ether.

CHLCBLCHLCH..domeinnamen, i i' delta delta disubstituted butyl ether.

In some of the examples set forth in the above list it will be noted that the substituents which are split 0E are attached directly to an aromatic nucleus The reaction is carried out as in Example 1. except that the temperature is increased as, for example, by working in an autoclave or bomb. The temperature necessary may be illustrated by the fact that in the case of pp' dichloro diphenyl ether, a temperature of about 500 F. for about one hour is necessary.

The proportion of sulphur to the polymers produced from the above compounds varies from 20 to 80 per cent, depending uponwhether the sulphur in the unit (IT-Siler] is a group of two, three, four, five or six sulphur atoms and also depending upon the molecular `weight of the disubstituted compound.

In the above group there are found formels,

l. ethers, thioethers, sulphones, alkoxy compounds and aryloxy compounds. In all, however, there are two carbon atoms joined to and separated by structure characterized by an ether linkage. 'I'his is a common quality running through the entire series. To' each of the said carbon atoms' there is joined a substituent lwhich is split oiI.

An ether linkage is dened as an oxygen or sulstructure characterized by an ether linkage in Owing to this common quality, the` polymers .produced from these compounds by reaction with an alkaline polysulphide have a number of outstanding and important properties -which distinguish them from the polymers produced from disubstituted ethylene and propylene, as already described. This is particularly true after the intermediate potentially reactive polymers have been cured, especially by heating with an oxidiz- .ing agent and an acid, as hereinafter more fully set forth, and the curing step will be illustrated by the following example:

The above ingredients are thoroughly mixed by mastication and then the resulting compound is cured by heating to about 300 F. for about one hour.

The distinguishing characteristics can be summarized as follows: I

(1) Elongation of over 200 per cent without rupture and retraction substantially to its original shape after such elongation.

(2) The ability to retain the above property at temperatures as low as about -30 F'.

(3) Ability to remain substantially unswollen by long immersion in gasoline, petroleum ether, lubricating oil and other parailin hydrocarbons.

(4) Ability to be only slightly swollen by long immersion in benzol, toluol and carbon tetrachloride.

It-has already been stated that the polymers of this invention may be produced not only by the alkaline polysulphide reaction but also by oxidizing polymercapto compounds. A specific illustration will be given as follows:

Example 3.-138 lbs. or 1 mol of dimercapto ethyl ether, SH.C2H4.O.C2H4.SH are dissolved in 100 gallons sodium hydroxide solution containing lbs. of NaOH: that is, an amount of NaOH slightly in excess of 2 mols. With this solution there is intimately mixed a freshly prepared suspension of magnesium hydroxide made by treating 10 lbs. of MgClzHnO with 2 gallons of water and adding thereto a solution of 4 lbs. NaOH dissolved in 0.5 gallon of water. The entire mixture is then placed in a reaction vessel provided with stirring means and also means for heating, for example, steam coils. The mixture is sub- .iected to stirring and to this is gradually added an oxidizing agent in the form of a solution of sodium polysulphide (made, for example, bydissolving 348 lbs. or 2 mois of sodium tetrasulphide in gallons of water) during a period of about ten minutes. The reaction occurs approximately at room temperature and is somewhat exothermic. The reaction is substantially completed after all the polysulphide has been added. The completion of the reaction is indicated by withdrawing a sample, acidifying itjmd observing whether the odor of mercaptan is absent. Stirring may be continued until the reaction is completed, as indicated by this test.

'I'he polysulphide acts as an oxidizing agent and converts the dimercapto ethyl ether into a complex polymer or plastic. 'I'he advantages of the magnesium hydroxide is that the said polymer or plastic is produced in the form of a latexlike liquid which has the unique property of being capable of intimate mixture with water and settling out subsequently by the action of gravity. This property permits intimate and thorough arenoso washing to remove soluble impurities. Acidlfication of the latex-like liquid causes the separation of polymer as an agglomerated mass, the removal of the impurities from which would be a dlicult problem. It is therefore'highly desirable to accomplish the washing while this mass is in dispersed form, inasmuch as under such conditions the high degree of dispersion of the polymer permits an extremely thorough removal of the soluble impurities by washing. 'The diiliculty of transporting the latex in agglomerated form, and the Vease `with which it sticks to parts of apparatus, such as the stirrer, also makes it advisable to produce the polymer in the reaction vessel in its dispersed latex-like form, from which vessel it'can be readily removed because of its iluid characteristics. If the polymer were produced in the reaction vessel in its coagulated rubbery form it would be difficult to remove it therefrom and it would be contaminated with the 'reagents used in its manufacture.'

Washing of the polymer in -its dispersed condition may be accomplished in the reaction vessel by stirring it up with successive quantities of water, 'settling and drawing oli the supernatant wash liquid. The washing can, of course, be accomplished in a different vessel. In any event, it is desirable to preserve the polymer in its .dispersed condition until after removal from the reaction vessel.

The washed latex is then transferred to a second vessel where coagulation or agglomeration is produced by acidification. Sumcient acid may be added for this purpose until the mother liquid is acid to methyl orange or brought to a pH of about 3. The coagulated polymer is then dehydrated by any suitable method, e. g. milling, mastication or kneading. In such processes, considerable heat is generated which, together with the mechanical action, causes the removal of water.

In the above example, instead of sodium hydroxide as the agent for dissolving the dimercapto compound, other alkaline hydroxides could be used, for example, potassium, ammonium, lithium, calcium, barium, strontium, and in general any other alkaline materials which will not form' highly insoluble sulphides.

Instead of magnesium hydroxide, other gelatinous hydroxides may be employed, for example, aluminum hydroxide, chromium hydroxide, ferric hydroxide. Dispersing agents other than hydroxides may be employed, for example, gelatin, albumin, casein, agar, soluble cellulose esters, etc.

Instead of sodium polysulphide, other polysulphides may be employed. e. g. potassium and ammonium polysulphide or any other soluble polysulphide. Other oxidizing agents may. be used, for example, oxygen, air,4 ozone, hypohalites, and in general any oxidizing agent effective lin an alkaline solution, for example, hydrogen peroxide-and metallic peroxides, perborates, chromates, dichromates, manganates and permanganates, etc. The reaction is preferably carried on under alkaline conditions because it has been found that the reaction is very favorably influenced by such conditions.

Although in the above example, the step of agglomerating or coagulating the polymer was specifically described, it is in some cases advantageous to preserve the polymer in its dispersed form, as such, e. g., for use in coating and impregnating various materials.

The product obtained vin this case is a white coagulum which, upon drying, is in thin sheets, a pale amber translucent and highly elastic solid. When compounded with an'oxidizing agent and an acid as hereinafter more` fully set forth, it undergoes transformation by heat. The transformed product is yhighly elastic and resistant to tear. `It is practically unaffected by immersion in gasoline over long periods and Will withstand exposure to benzene.

One of the important properties of the product of this invention is its capacity to be trans.

formed by heat into a plastic or product having valuable commercial properties.

The following is a' specic illustrative example of the Lcuring or transformation of the intermediate polymer produced as in Example 3 into its final state by heating with an oxidizing agent These ingredients are thoroughly mixed and then subjected to a temperature of 290 F. for 60 minutes or 300 F. for 30 minutes.

lows:

Tensile strength: About 1700#/sq. in.

Elongation at break; About 500%.

Temperature resistance: Will not become'inflexible above 45 1i'.v Will stand about 200 F.

, continuously.

Solvent resistance: Substantially unaffected by water, gasoline, paramn hydrocarbons, dilute acids and alkalies. Very slightly affected by solvents, such as benzol, toluol, xylol. Unaifected by alcohol, acetone andesters.

Tear and abrasion resistance: Excellent.

Electrical properties: Closely approaching those of natural rubber.

Stability: Substantially unaffected by age or sunlight. Uniquely. resistant to ozone, oxygen, or

air. l

Eifect of' gases: Highly resistant to diffusion. About 40 times less permeable than natural rubber.

The product produced as in Examples 3 and 4 is a cured polymer of the unit whereas that prepared as in Examples' 1 and 2 is a cured polymer of the unit A comparison ofthe physical properties of the respective products shows the advantages of the former over the latter.

In E'xample 3, any of the compounds herein above or herein below listed, where X and X"v signify -SI-I groups, can be substituted for the dimercapto ethyl ether.

'I'he compound produced as in Example 3 is substantially a polymer of the unit ple 3, but also by removing the labile sulphur from the tetrasulphide polymer produced as in Example 1. -This will be specifically illustrated by the following example:

The properties of the cured product are as fol- Example 5.-Proceed as in Example 1 up to but not including the step of coagulation. Add 250 kilograms (6.25 kilogram mois) of NaOH dissolved in 500 liters of water, raise the temperature to 212 F. and maintain there for about 30 minutes. 'I'hen cool, settle and proceed as in Example 1 to wash the latex and lcoagulate the polymer. Ins'tead of NaOH numerous other desulphurizing agents can be used, e. g. sodium sulphide, sodium sulphite, sodium hydrosulphide, sodium acid sulphite, etc. In this Example 5, any of the organic compounds herein listed may be substituted for the BB' dichlor ethyl ether' (using the same molecular proportions), X and X being substituents split off during the reaction. y

The advantages to be obtained by opening up the space between the reactive carbon atoms and placing therein structure characterized by an ether or ether-like linkage may be illustrated by the following comparative table wherein the prop' erties of cured polymers made by reacting (A) ethylene dichloride and (B) BB' dichlor Vethyl ether, respectively, with an alakline polysulphide are set forth, the tetrasulphide polymer being referred to in each case and all conditions being the 'same except the nature of the structure intervening between the reactive carbon atoms. The intermediate polymer was produced by the process in Example 1 and was cured as in Example 2.

Tensile strength 630lbs./sq. in l,l50lbs./sq. in. Elongation at break... o 500 Temperature resist- Brittle at +5 F... Brittle at -40 F.

ance. Odor..-.. Bad Practically odorless.

Having explained the advantages to be obtained by inserting structure characterized by an ether linkage, the invention will be further described by illustrating various other intervening structure.

b. Intervenina structure characterized by lA specic example for the purpose of illustration is a reaction between an alkaline polysulphide and 1,4 disubstltuted butene 2 XCHLCH: CH.CH2.X'

This reaction is specifically described as follows:

Example 6.--Proceed as in Example 1, substituting 1,4 dichlorobutene 2 for BB' dichlor ethyl ether, in the same molecular proportions.

In the above,example, instead of 1,4 dihalogenated butene 2, any member selected from the following list can be employed, using thesame molecular proportions.

Table 2 disubstituted 3 tolyl propene 2.

. x.cH2.cH=cH.cH2cH2.x' disabstituted pentene 2.

xcm.cn=cn.cm,cm.cmx' v substituted hexene 2.

x.cm.cm.cH=cH.cH2.cm.cHzx' xcmcmcrhcncmcmx' 1,6 substituted hexene 3.

monaco 1,4 disubstituted pentene 2. d H, IJ.CH2.CH=CH.CH2. IJH.CHJ

x a x' 1,6 disubstituted heptane 3.

In all of the above compoundsihere are twol carbon atoms joined to and separated by structure characterized by unsaturated hydrocarbons. This is a common quality running through the entire series. lTo each of the said carbon atoms there is joined a substituent which is split off dur- .ing the reaction.

Owing to this common quality the polymers produced from these compounds by reaction with an alkaline polysulphide have a number of outstanding and important properties, as already described, which distinguish this compound from the polymers produced from disubstituted ethylene and propylene. 'I'his is particularly true after the intermediate potentially reactive polymers have been cured by heating with an oxidizing agent and an acid, and the curing step will be illustratedby the following example:

Example 7 Parts by weight Polymer produced as in Example 6 100.00 Zinc oxide 10.00 Stearic avid 0.05 Benzothiazyl disulphide 0.25 Carbon black 60.00

Tensile strength: 1000 iba/sq. in.

Elongation: 400%.

Permanent set: 5%. v

Ability to retain the above properties at temperatures as low as 40 F.

Not swollen by long immersion in paraffin hydrocarbons.

Only slightly swollen by long immersion in benzol,

toluoland carbon-tetrachloride.

Not affected by ozone.

Per cent sulphur: 71.00.

'I'he compound produced, as in Example 6, is substantially a polymer of the unit It can be partially desuiphurized as taught in Example 5 and converted into a compound which is substantially a polymer of the unit and the latter polymer can also be produced as taught in Example '3, i. e. by the mercaptan reaction, using 1,4 dimercapto butene (instead of dimerca'pto ethyl ether). Any ot' the compounds in the above Table 2, where X and X' are -SH groups, can be used instead of the dime'rcapto ethyl ether of Example 3.

c. Interceming structure characterized by saturated carbon atoms This is illustrated by the following compound:

[X.CH2.CH2.CH2.X'] where X and X are substituents capable of being split ofi by reaction with an alkaline polysulphide.

This compound may be substituted for the ether of Example 1 in the same molecular proportion. The resulting compound is substantially a polymer of the unit It can be partially desulphurized as in Example 5 and convered into a compound which is substantially a polymer of the unit [-CHaCHa-CIjIa-Sa-l y This compound can be also produced by the mercaptan reaction as taught in Example 3. The polymers so produced may be cured as taught in Examples 2, 4 and 7.

One of the advantages of such polymers over those obtained from compounds like ethylene or propylene dichloride is freedom from the disagreeable odor of the latter.

Instead of the specic compound above mentioned others that may be employed are as follows:

X.(CH2) 4X' thus producing a series of compounds which are substantially polymers of the unit where n is greater than 2. As n increases, the elasticity of the cured and uncured polymers decreases and the ductility increases, in general.

d. Intervemng structure characterized by aromatic or aryl structure This is illustrated by the following compound:

Where X and X' are substituents capable of being split off by reaction with an alkaline polysulphide. This compoundvmay be substituted for the ether of Example 1 in the same molecular proportion. The resulting compound is substantially a polymea` of the unit It may be partially desulphurized as in Example 5 and converted into a polymer which is substantially 4a polymer of the unit Example 8.-To one liter of 2 molar sodium tetrasulphide add a suspension oi Mg(OH) 2 made by dissolving 25 grams oi crystallized magnesium chloride in ce. of water and adding a solution of 10 grams of NaOH in 50 cc. water. Add about one m01 (150 grams) of para dichlor benzene. Place the mixture in an autoclave, preferably provided with a stirrer, and heat to about 300 C. for about 10 hours. Cool to room temperature and proceed further as taught in previous examples.

Instead of paraxylene dichloride or paradh chlorbenzene, other compounds may be selected, as for example, any of those shown in Table 3 below.- For the reaction with alkaline polysulphide, X and X' are substituents capable of being` split 01T during said reaction. For the mercaptan reactions, X and X are -SH groups:

Table 3 xon disubstituted ortho xylene.

X.CH2.CH CHLCHLX pp" disubstituted diethyl benzene.

aa disubstituted naphthalene.

bb' disubstituted naphthalene.

XCH

H 1,3 disubstituted mesimene.

CHX

disubstituted 1,4 dimethyl naphthalene.

DD' disubstituted dibenzyl. f

aa disubstituted anthracene.

disubstituted para ethyl butyl benzene.

x.CH.CHLQHOCHLCHLCHLH.omen,

disubstituted para hexyl propyl benzene.

In all of the above examples there are two carbon atoms joined to and separated by aromatic structure or structure characterized by an aromatic or aryl group or groups. This is a common quality running through the entire series.

Owing to this common quality the polymers produced from these compounds have a number of outstanding and important properties, as already described, winch distinguish them `from the polymers produced fromdisubstituted ethylene and propylene. This is particularly true after the intermediate potentially reactive polymers have been cured by heating with an oxidizing agent and an acid, and the curing step will be illustrated by the following examples:

' Example 9 Part by weight Polymer produced from paradichlor xylene 100.00 Zinc oxide 10.00 Stearic acid 0.05 Benzothiazyl disulphide 0.25 Carbon black 60.00

The above ingredients are thoroughly mixed by mastication, as for example, on rubber mixing rolls and the resulting compound is cured by I heating to about 300 F. for about 1 hour. Instead of zinc oidde other oxidizing agents can be used in the above formula, e. g. oxides of copper,

lead, bismuth, antimony, arsenic, manganese and chromium. Organic oxidizing agents including benzoyl peroxide and trinitro benzo can also be used.

All such polymers may be compounded and cured as in Example 9. When the compound made from disubstituted para xylene is so cured, it develops properties which may be contrasted with those obtained by curing a polymer made from a compound having no intervening structure, e. g. ethylene dichloride, as shown by the following table. `AJ1 compounding, curing and .other conditions are the same, the diierence bel ing that caused by introducing the benzene ring between the carbon atoms of ethylene dichloride. The intermediate polymer was made by the process of Example 1 and cured by the process of Example 2.

Polymer from Polymer from eene para dichlor di ride xylene Temuestrengt asoma/sain sonoma/541.111. Elongation 500% 10 odnr Bad Ogrless or pleasant or.

In general, the introduction of aromatic structure between the reactive carbon atoms, (i. e.,

the carbon atoms to which are attached the sub- Y stituents split off during reaction with alkaline polysulphide Where the polysulphide reaction isused, or the carbon atoms to which SH groups are attached where the mercaptan reaction is used) produces products of a hard nature, having in many cases high tensile strength and great elasticity but low elongation.

Enough illustration has been supplied to make apparent the profound iniiuence of the intervening structure and to make apparent the fact that the invention lis not limited to the particular classes of such intervening structure specifically mentioned.

PoLYMms Fou COMPOUNDS WHERE THE CARBON Arons n; 'rms Foimm -f C ABE ADJA- cEN'r Ann CoNNEc'rEn nx A VmNcn Bonn .These are polymers of the unit ifi-sm] i and may be produced by substituting in Example 1 above, in the same molecular proportions shown therein, a compound having two adjacent carbon atoms to each of which is attached a substituent which is split oiI during the reaction, as illustrated by the following list:

Table 4 disubstituted ethane.

Hz Ha X.C`C.CH: 1,2 disubstituted propane.

resent mercapto (SH) groups,- and by reaction with sulphur, as already explained, said disulphide polymers canbe converted into the correspending tri, tetra-,penta-{and hexasulphide polymers.

CURING 'rma INTERMEDIATE Pnonuc'rs Having thus disclosed the wide scope of the intermediate polymers that may be employed according to the present invention, the curing of those polymers will now be more fully described.

A typical example of the curing of a polymer in accordance with the present invention is as fol- These products are incorporated by suitable lows:

` Example 10 Parts by Iweight Polymer produced as in Example 1 100 Zinc oxide 10 Carbon black 60 Benzoic acid- 1 mastication, as, for example, on rubber mixing rolls, and the resulting compound is then cured` by heating to approximately 300 F. for 20 minutes to an hour.

In the above example, instead of zinc oxide. any of the following curing agents may be employed:

Arsenic pentoxide Antimony pentoxide Bismuth tetroxlde Manganese peroxide Ferrie oxide Nickelic oxide Cupric oxide Silver oxide Barium peroxide Mercurio oxide Stannic oxide Lead peroxide Lead monoxide (Instead of the above the corresponding droxides that exist may be used.)l

Lead arsenate Ferrie chromate Potassium ferri cyanide Zinc ferri cyanide Mono nitro benzene Di nitro benzene Tri nitro benzene Cupric stearate Cupric laurate Cupric acetate Lead stearate Lead oleate Lead laurate Lead caproate Zinc stearate Mono nitro toluol Zinc laurate Di nitro toluol 1' Zinc caproate Mono nitro naphthalene Zinc acetate Di nitro naphthalene Benzoyl peroxide Mono, di and tri nitro phenol (picric acid) Ammonium persulphate Zinc propionate Zinc thiocyanate Zinc benzoate Zinc chromate Lead chromate Abietic acid Benzilic acid acetic acid Citric acid Butyric acid Hydrochloric acid Caproic acid Hydrobromic acid Lauric acid Aminosulphonic acid Stearic acid Sulphanilic acid Arsenic acid Tartaric acid Thio benzoic acid Benzoic acid Acrylic acid Malonic acid Oleic acid Zinc chloride Stearic acid Aluminum chloride Malic acid Ferric chloride Succinic acid Ferrous chloride Stannous chloride Antimony chloride Cinnamic acid Propionic acid Benzoyl benzoic acid Instead of the chlorides, the corresponding bromides or fluorides may be used.

Under the conditions of cure, although the. substances are in a condition which may be described by the term dry from the practical point of view, traces of moisture are nevertheless always present and it is the hydrogen ion or acidic hydrogen and not the specic acid or acid-engendering substance which is the source of this ion which, in conjunction with the oxidizing agent, is responsible for the curing reaction which occurs in accordance with the present invention.

One of the functions of the acidic hydrogen or hydrogen ion in conjunction with the oxidizing agent is to produce an increased tightness of (b) The same polymer cured with a curing agent in the absence of the hydrogen ion.

Case a is illustrated by a product produced in accordance with Example 10 above.

Case b is illustrated by the product made in the same way but omitting the benzoic acid.

Tensile strength lha/sq. in.. Y l Percent elongation before break..

Percent of {siemenen set Hardness hors duroxneter) In addition, compound a hasV an abrasion resistance substantially double of compound b and is therefore much more stable against deteriorating influences, such as action of solvents,

ozone, sunlight.

This comparison is all the more favorable to compound a because compound b was cured for a period of one hour, as compared with a twenty minute cure for compound a.. If compound b had been cured for only twenty minutes the properties mentioned would have been much poorer.

In several of the examples of the present invention, benzothiazyl disulphide is used, the primary function of which is to cause softening of the polymer and thereby facilitate compounding. It also increases somewhat the rate 4of curing.

Instead of acids per se substances which gencrate an acid under the conditions of cure may be used. For example, in the case of the organic acids Kabove mentioned, the corresponding nitriles may be used because they are decomposed Aduring the curing and yield the corresponding acids.`

Benzoic acidhas been'l found to give particularly good results including increased resistance to water.

' I claim:

1. A composition of matter capable of being cured when heated comprising a polymer of the lunit where represents structure 'selected from the group consisting of two adjacent carbon atoms connected by a valence bond and two carbon atoms separated by and joined to intervening structure, incorporated with a metallic oxide and a substance which provides an acid under the conditions of curing.

2. A composition of matter capable of being cured when heated comprising a polymer of the unit [- (i2-sl lo l] where with an oxidizing agent and a substance which provides an acid under the conditions of curing.

3. A composition oi matter capable 'of `being cured when heated comprising a polymer of represents two carbon atoms separated by and joined to intervening structure, incorporated with a metallic oxide and a substance which provides an acid under the conditions of curing.

4. The process which comprises heating a polymer of the unit represents structure selected from the groups consisting of two adjacent carbon atoms'connected by a valence bond and two carbon atoms separated by and joined to intervening structure, with an oxidizing agent and a substance where where which provides an acid under the conditions of.

curing.

5. The process which comprises heating polymer of the unit J- :....t-s....] where f I I represents structure selected from the groups consisting of two adjacent carbon atoms connected by a valence bond and two carbon atoms separated by and joined to intervening structure, with a metallic oxide and a substance which provides an acid under the conditions of curing.

6. The process which comprises heating a polymer of the unit JIJ-Brut] where f I represents two carbon atoms separated by and joined to intervening structure, with an oxidizingagent and a substance' which provides an acid under the conditions ofcuring.

7. The process which comprises heating a polymer of the unit JIJ-sts] a .-t l I l represents two carbon atoms separated by andv joined to intervening structure, with a metallic where oxide and a substance which provides an 4acid under the conditions of curing.

8. A composition of matter resulting from the' heating of a polymer of the unit where represents structure selected fromrth'e groups consisting of two adjacent carbon atoms connected by a valancebond and4 two carbon atoms separated by and Joined to intervening structure, with an oxidizing agent and a substance which provides an acid under the conditions of curing.

9. A composition of matter resulting from the heating of a polymer oi the unit heating of a polymer ot the, unit [-Jll -fslul] t i I I represents-twocarbon atoms separated`by and where where joined to intervening structure, with arr oxidizing agent and a substance which providesan acid under .the conditions of curing.

11. A composition otm'atter resulting'from the heating oi' a polymer of the unit represents two carbon atoms separated by and joined to intervening structure, with a metallic oxide and asubstance which under the conditions of curing.

where 12. A composition of matter resulting from the heating of a polymer 'of the Vunit v where' represents vtwo carbon atoms separated by and Joined to intervening structure, with a metallic oxide and `benzoic acid.

13. A composition of matter resulting from the heating of apolymer of the unit' y (El-Ba t t;

represents two carbon atoms separated by and joined to intervening structure. with a metallic oxide and thio benzoic acid. y

14. A composition of matter resulting vfron; the heating of a polymer of the unit i [...lsmilssij represents two carbon 'atoms separated by and joined to interveningstructure, with a metallic oxide and zinc' chloride. 'Y

where provides an acid 15. A composition of matter comprising a polymer of the unit H----sw] where where represents structure selected from the group consisting of two adjacent carbon atoms connected by a valence bond and two carbon atoms separated. by and joined to intervening structure, ,incorporated with a difticultly water soluble inorganic oxide and an acid.

17. A composition of matter resulting from the heating of a polymer oi' the unit H; t-smf] represents structure selected from the group consisting of two adjacent carbon atoms connected by a valence bond and two carbon atoms separated by and joined to intervening structure, with a difllcultly water soluble oxide and an acid.'

18. A composition of matter resulting from the heating of a polymer of the unit represents structure selected from the group consisting of two adjacent carbon atoms connected by a valence bond and two carbon atoms separated by and joined to intervening structure, with a diiiicultly water soluble inorganic oxide and an acid.

where where JOSEPH C. PATRICK. 

